TW202313552A - Plasticizer composition comprising tripentyl esters of 1,2,4-cyclohexanetricarboxylic acid - Google Patents

Abstract

The present invention relates to a plasticizer composition comprising a compound according to the following formula (I)

wherein the radicals R ₁, R ₂and R ₃are each independently selected from the group consisting of n-pentyl, 2-methylbutyl and 3-methylbutyl. The present invention further relates to the use of the plasticizer composition as plasticizer for polymers and a plastic composition comprising the plasticizer composition.

Description

Plasticizer composition comprising tripentyl ester of 1,2,4-cyclohexanetricarboxylic acid

(I) 其中基團R ₁、R ₂、及R ₃各自獨立地選自由正戊基、2-甲基丁基、及3-甲基丁基所組成的群組。本發明進一步關於該塑化劑組成物作為用於聚合物的塑化劑之用途以及包含該塑化劑組成物的塑膠組成物。 The present invention relates to plasticizer compositions comprising compounds according to the following formula (I),

(I) wherein the groups R ₁ , R ₂ , and R ₃ are each independently selected from the group consisting of n-pentyl, 2-methylbutyl, and 3-methylbutyl. The invention further relates to the use of the plasticizer composition as a plasticizer for polymers and to plastic compositions comprising the plasticizer composition.

Plastics and polymers are integral to most applications. Polyvinyl chloride (PVC) is one of the most economically significant plastics and is used both in the form of hard PVC and in the form of soft PVC. Since many plastics and polymers are in many instances too brittle or difficult to process, plasticizers or plasticizer compositions are added to plastics in many applications in order to adjust their properties.

In the manufacture of PVC-based products such as floor coverings, toys, etc., the addition of plasticizers to PVC improves processability and further adjusts use-related properties. Due to their favorable properties, some of the most important plasticizers for PVC and vinyl chloride copolymers are still derived from phthalates (especially diethylhexyl phthalate (DEHP), diisophthalic acid Compounds from the group of nonyl esters (DINP), and diisodecyl phthalate (DIDP). Due to discussions about the possible toxic effects of this substance class, a search has been made for alternatives to phthalate-based plasticizers for many years.

Many possible substitutes have been described in the prior art, such as 1,2- or 1,4-cyclohexanedicarboxylates, which can be prepared by phthalate or ring hydrogenation of terephthalate. Other plasticizers are also known and described in the relevant literature.

It is an object of the present invention to provide plasticizers which can be used as substitutes for phthalate-based plasticizers. These plasticizers should have a processability with polymers, especially with PVC and vinyl chloride copolymers, at least at the level of DINP and preferably even higher. Specifically, these novel plasticizers should have a low tendency to migrate out of plasticized PVC or plasticized vinyl chloride-containing copolymers into other substances.

This basic goal is achieved by the plasticizer presented in Claim 1 of the scope of application. Preferred specific examples are specified in the appended claims.

(I) 其中基團R ₁、R ₂、及R ₃各自獨立選自由正戊基、2-甲基丁基、及3-甲基丁基所組成的群組。基團R ₁、R ₂、及R ₃因此獨立地係三種可能的異構C5-烷基基團之一。 The present invention provides plasticizer compositions comprising at least one compound according to the following formula (I):

(I) wherein the groups R ₁ , R ₂ , and R ₃ are each independently selected from the group consisting of n-pentyl, 2-methylbutyl, and 3-methylbutyl. The groups R ₁ , R ₂ , and R ₃ are thus independently one of three possible isomeric C5-alkyl groups.

(II)

(III)

(IV) In a particularly preferred embodiment of the invention, the groups R ₁ , R ₂ , and R ₃ are the same. This means that the groups R ₁ , R ₂ , and R ₃ all correspond to the same alkyl group, i.e. R ₁ = R ₂ = R ₃ = n-pentyl or R ₁ = R ₂ = R ₃ = 2-methyl butylbutyl or R ₁ = R ₂ = R ₃ = 3-methylbutyl. The compounds thus obtained are compounds (II), (III), and (IV) shown below. Compound (II) means a compound wherein R ₁ = R ₂ = R ₃ = n-pentyl, compound (III) means a compound wherein R ₁ = R ₂ = R ₃ = 2-methylbutyl, and compound ( IV) means compounds in which R ₁ =R ₂ =R ₃ =3-methylbutyl. In a preferred embodiment of the present invention, the plasticizer composition comprises at least one of compounds (II), (III) or (IV).

(II)

(III)

(IV)

Surprisingly, it has been found that the plasticizer compositions according to the invention have improved properties, for example with respect to gelling behavior, viscosity, and Shore hardness. When using the plasticizer composition in plastisols and dryblends, it surprisingly exhibits improved processability compared to acyclic hydrogenated 1,2,4-benzenetricarboxylates.

The plasticizer compositions according to the invention are also particularly concerned with mixtures of compounds according to formula (I) above. wherein the groups R ₁ , R ₂ , and R ₃ may bear different isomeric alkyl groups and/or wherein the specific alkyl groups may also appear in different positions in one of R ₁ , R ₂ , and R ₃ In the example of a mixture of different compounds above, a plurality of different compounds according to formula (I) may thus be present in the mixture. Accordingly, the mixture is described below by the ratio of its respective alkyl groups based on all compounds according to formula (I) present in the mixture. The ratio of the respective alkyl groups can be determined by ¹ H-NMR. In the context of the present invention, it is understood that the groups R ₁ , R ₂ , and R ₃ may always have the same definition, that is, in each instance independently selected from n-pentyl, 2-methylbutyl, and 3 - the group consisting of methylbutyl.

(I) 其中來自由正戊基、2-甲基丁基、及3-甲基丁基所組成的群組的一個烷基基團係以30至95 mol%的比例且來自所具體指出的群組的另外一個烷基基團或另外兩個烷基基團係以5至70 mol%的比例存在於該混合物中，在各個例子中基於所有根據式(I)的化合物之所有基團R ₁、R ₂、及R ₃。此意指（例如）正戊基以30至95 mol%的比例且2-甲基丁基及/或3-甲基丁基以5至70 mol%的比例存在於該混合物中，基於式(I)之化合物之所有基團R ₁、R ₂、及R ₃。 The plasticizer composition according to the invention therefore preferably comprises a mixture of compounds according to formula (I)

(I) wherein an alkyl group from the group consisting of n-pentyl, 2-methylbutyl, and 3-methylbutyl is in a proportion of 30 to 95 mol % and from the specified A further alkyl group or two further alkyl groups of the group are present in the mixture in a proportion of 5 to 70 mol %, based in each case on all radicals R of all compounds according to formula (I) ₁ , R ₂ , and R ₃ . This means that, for example, n-pentyl groups are present in the mixture in a proportion of 30 to 95 mol % and 2-methylbutyl and/or 3-methylbutyl groups in a proportion of 5 to 70 mol %, based on the formula ( All groups R ₁ , R ₂ , and R ₃ of the compound of I).

Based on the above proportions of 30 to 95 mol % for one of the three specified alkyl groups and 5 to 70 mol % for one of the other two alkyl groups or for the other two alkyl groups, for each The following proportions of other possible alkyl groups can for example result in mixtures of compounds according to formula (I), based on all radicals R ₁ , R ₂ , and R ₃ : n-pentyl/mol% 2-Methylbutyl/mol% 3-Methylbutyl/mol% 50 50 - 50 50 40 30 30 34 33 33 47 3 50 95 5 0

Particularly preferred for the purposes of the present invention are plasticizer compositions comprising a mixture of compounds according to the abovementioned formula (I), wherein the mixture is present in a proportion of 40 to 95 mol % from n-pentyl A group consisting of 2-methylbutyl, 2-methylbutyl, and 3-methylbutyl with a proportion of 5 to 60 mol% of another group or two other groups from the specified group Groups, in each case based on all groups R ₁ , R ₂ , and R ₃ of compounds according to formula (I).

According to the invention, it is further preferred that the proportion of 2-methylbutyl groups is limited. Accordingly, a preferred plasticizer composition is a plasticizer composition comprising a mixture of compounds according to the above formula (I) in which the 2-methylbutyl groups are present in a proportion of at most 60 mol %, preferably in A proportion of at most 40 mol %, particularly preferably at most 20 mol %, is present in the mixture in each case based on all radicals R ₁ , R ₂ , and R ₃ of the compound according to formula (I).

The compounds of the above formula (I) according to the present invention can be prepared by various methods. In principle, esterification of 1,2,4-cyclohexanetricarboxylic acid with the corresponding alcohols n-pentanol, 2-methylbutanol, and 3-methylbutanol gives formulas (I), (II ), (III), and (IV) compounds would be possible. If it is desired to prepare mixtures of compounds according to the above formula (I), such mixtures can be obtained by esterifying with a suitable alcohol mixture consisting of the related alcohols n-pentanol, 2-methylbutanol, and 3-methylbutanol. Chemical 1,2,4-cyclohexanetricarboxylic acid to manufacture. The process conditions for the esterification of cyclohexane polycarboxylic acid derivatives are known in principle to those skilled in the art to which the invention pertains.

A further possible process for the preparation of compounds of formula (I) above is the transesterification of triesters of 1,2,4-cyclohexanetricarboxylic acid. In this example, it is preferred to use triesters whose respective alkyl groups are compared to the C5-alkyl groups present here n-pentyl, 2-methylbutyl, and 3-methylbutyl have a lower number of carbon atoms. One example of this would be the trimethyl ester of 1,2,4-cyclohexanetricarboxylic acid. For the preparation of compounds according to the above formulas (II), (III), and (IV), subsequent transesterification of 1,2, Trimethyl ester of 4-cyclohexanetricarboxylic acid. To prepare mixtures of compounds according to formula (I) above, appropriate alcohol mixtures consisting of the relevant alcohols n-pentanol, 2-methylbutanol, and/or 3-methylbutanol can be transesterified 1,2,4 - trimethyl cyclohexanetricarboxylic acid. The process conditions for the transesterification of cyclohexane polycarboxylate derivatives are known in principle to those skilled in the art to which the invention pertains.

A further possible method for the preparation of compounds of formula (I) above is the ring-hydrogenation of the corresponding esters of 1,2,4-benzenetricarboxylic acid. In this example, tripentyl 1,2,4-benzenetricarboxylic acid is used as the reactant, where each pentyl group can independently be n-pentyl, 2-methylbutyl, and 3-methylbutyl A group corresponding to the compound to be prepared according to the above formula (I). To prepare mixtures of compounds according to the above formula (I), suitable mixtures of the tripentyl esters of 1,2,4-benzenetricarboxylic acid are then used, based on the ratio of the respective alkyl groups. The process conditions for the ring-hydrogenation are known in principle to those skilled in the art to which the invention pertains, for example from EP 1 511 562 A1. 1,2,4-Benzene tricarboxylates were previously obtained by esterification or transesterification of 1,2,4-benzenetricarboxylic acid or 1,2,4-benzenetricarboxylic anhydride or 1,2,4-benzenetricarboxylic acid Trialkyl esters are prepared concomitantly (see eg EP 3 147 318 A1).

Besides at least one compound according to the abovementioned formula (I) or a mixture of compounds according to the formula (I), the plasticizer composition according to the invention may also comprise further plasticizers. Depending on the purpose of use, one or more further plasticizers may be present in the plasticizer composition, in particular different from the compounds according to formula (I) above, in order to specifically adjust the properties of the resulting plasticizer composition. However, according to a particularly preferred embodiment, the plasticizer composition comprises less than 5% by weight, more preferably less than 0.5% by weight, especially less than 0.1% by weight of phthalate.

The additional plasticizer may in principle be selected from the group consisting of adipates, benzoates such as monobenzoates or diol dibenzoates, chlorinated hydrocarbons (so-called chlorinated paraffins), citrates, Cyclohexyl dicarboxylate, epoxidized fatty acid ester, epoxidized vegetable oil, epoxidized acylated glyceride, furan dicarboxylate, phosphate, succinate, sulfonamide, sulfonate, terephthalate, The group consisting of 1,2,4-benzenetricarboxylates, and oligoesters or polyesters based on adipic acid, succinic acid, or sebacic acid. In a preferred embodiment of the present invention, the plasticizer composition comprises C4- C6-acid, trialkyl citrate, acetylated trialkyl citrate, diol dibenzoate, trialkyl 1,2,4-benzenetricarboxylic acid, dialkyl terephthalate , dialkyl phthalates, esters of furandicarboxylic acid, dialkyl esters of dianhydrohexitol (such as isosorbide), epoxidized fatty acid alkyl esters, polymer plastics Further plasticizers from the group consisting of polyadipate, and dialkyl esters of 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid.

In a more preferred embodiment, the additional plasticizer present in the plasticizer composition is selected from the group consisting of C8- to C13-alkyl benzoate, C4- to C10-dialkyl adipate, Neopentylthritol tetrapentanoate, acetylated trialkyl citrates with C4 to C9-alkyl groups, C4- to C10-trialkyl 1,2,4-benzenetricarboxylates, terephthalate C4- to C9-dialkyl phthalates, C4- to C13-dialkyl phthalates, especially C9- to C13-dialkyl phthalates, and 1,2-, 1,3- or 1, The group consisting of C4- to C10-dialkyl esters of 4-cyclohexanedicarboxylic acids.

The present invention preferably provides a plasticizer composition comprising at least one compound according to the above formula (I) or a mixture of compounds according to the above formula (I) and di-ethylhexyl terephthalate (DEHT or DOTP) . The corresponding plasticizer compositions are notable for their low volatility. Since the products comprising such plasticizer compositions have low release values, the corresponding plasticizer compositions are useful in a particularly advantageous manner for interior applications.

The present invention preferably provides a plasticizer composition comprising at least one compound according to the above formula (I) or a mixture of compounds according to the above formula (I) and 1,2- or 1,4-cyclohexanedicarboxylate acid ester, specifically the corresponding diisononyl ester or di-2-ethylhexyl ester. Products comprising such plasticizer compositions are notably characterized in that, in addition to low volatility, they also have improved cold flexibility. In addition, since the plastisol containing the corresponding plasticizer composition has a lower viscosity, it has better processability. At the same time, they exhibit excellent UV stability, so they can be advantageously used both indoors and outdoors.

Also preferred is a plasticizer composition comprising at least one compound according to the above formula (I) or a mixture of compounds according to the above formula (I) and a trialkyl ester of 1,2,4-benzenetricarboxylic acid , wherein the alkyl groups have 6 and more carbon atoms, preferably 7, 8, 9, 10 or 11 carbon atoms. Corresponding plasticizer compositions or products produced therefrom have particularly low volatility.

The present invention preferably provides a plasticizer composition, which comprises at least one compound according to the above formula (I) or a mixture of compounds according to the above formula (I) and selected from dibutyl terephthalate, di(terephthalate) Iso)pentyl ester, isodecyl benzoate, isononyl benzoate, acetyl tributyl citrate, tributyl citrate, dipropylene glycol dibenzoate, diethylene glycol dibenzoate, Rapid gelling plasticizers of the group consisting of triethylene glycol benzoate and mixtures of two or more thereof. These fast gelling plasticizers ensure improved processability in plastisol applications such as floor coverings, artificial leather, or wall coverings.

Plasticizer compositions according to the invention comprising compounds according to the above formula (I) or mixtures of compounds according to the above formula (I) with or without further plasticizers can be used as plasticizers for the plasticization of plastics or polymers agent. This use as a plasticizer for polymers is another part of the object of the present invention.

Suitable polymers are preferably selected from polyvinyl chloride (PVC), homopolymers or copolymers based on: ethylene, propylene, butadiene, vinyl acetate, glycidyl acrylate, glycidyl methacrylate esters, ethyl acrylate, acrylate or butyl methacrylate with alkoxy groups of branched or unbranched alcohols containing one to ten carbon atoms, acrylonitrile or cycloolefins, chlorosulfonated polyethylene, poly Vinylidene chloride (PVDC), polyacrylates, especially polymethylmethacrylate (PMMA), polyalkylmethacrylates (PAMA), polyureas, silylated polymers, fluoropolymers, especially Polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl acetate (PVAc), polyvinyl alcohol (PVA), polyvinyl acetal, especially polyvinyl butyral (PVB), polystyrene Polymers, especially polystyrene (PS), expandable polystyrene (EPS), acrylonitrile styrene acrylate (ASA), styrene-acrylonitrile (SAN), acrylonitrile butadiene styrene (ABS) , styrene-maleic anhydride copolymer (SMA), styrene-methacrylic acid copolymer, polyolefins, especially polyethylene (PE) or polypropylene (PP), thermoplastic polyolefins (TPO), polyethylene-acetic acid Vinyl ester (EVA), polycarbonate, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyoxymethylene (POM), polyamide (PA), polyurethane ( PU), thermoplastic polyurethane (TPU), polysulfide (PSu), biopolymers, especially polylactic acid (PLA), polyhydroxybutyraldehyde (PHB), polyhydroxyvaleric acid (PHV), polyester , starch, cellulose and cellulose derivatives, especially nitrocellulose (NC), ethyl cellulose (EC), cellulose acetate (CA), cellulose-acetate/butyrate (CAB) , rubber, and polysiloxane group.

The plasticizer composition according to the invention is preferably used as a plasticizer for PVC or vinyl chloride-containing polymers.

The present invention further provides a plastic composition comprising one or more polyvinyl chloride (PVC), copolymers of vinyl chloride and vinyl acetate or butyl acrylate, polyalkyl methacrylate (PAMA), poly Polymers of the group consisting of vinyl butyraldehyde (PVB), polyurethane, polysulfide, polylactic acid (PLA), polyhydroxybutyraldehyde (PHB), and nitrocellulose and according to the invention comprising Plasticizer compositions of compounds of the above formula (I) or mixtures of compounds according to the above formula (I) with or without further plasticizers. The preferred polymer in the plastic composition is PVC. The PVC is preferably suspension PVC, bulk PVC, microsuspension PVC, or emulsion PVC. Regarding the parts by mass of the individual components, it is preferred according to the invention that the plastic composition comprises 5 to 200 and preferably 10 to 150 parts by mass of the plasticizer composition according to the invention per 100 parts by mass of polymer.

The following are also advantageous: the plastic composition according to the invention not only comprises the one or more polymers and the plasticizer composition according to the invention but also one or more compounds from heat stabilizers, fillers, pigments, foaming Additives for the group of agents, biocides, UV stabilizers, light stabilizers, co-stabilizers, antioxidants, viscosity modifiers, degassers, adhesion promoters, lubricants, and colorants. The plastic composition according to the present invention preferably includes a thermal stabilizer and preferably optionally includes fillers and pigments.

The plastic compositions according to the invention can be used in adhesives, sealing compounds, coating materials, paints, inks, plastisols, foams, synthetic skins, floor coverings (e.g. roofing or foam layers), roofing membranes, underwater hulls Protective compounds, fabric coatings, cables, wire insulation, hoses, extruded products, films, for automotive interior parts, for wall coverings, liquid inks, toys, contact sheets, food packaging or pharmaceutical products such as Tubes or blood bags.

The present invention is described below with reference to examples. These examples are illustrative and should not be construed as limiting. Embodiment 1: Preparation according to the plasticizer of the present invention

432 g of 1,2,4-cyclohexanetricarboxylic acid (2.0 mol; Suzhou Rovathin Foreign Trade Co. Ltd., purity (NMR) > 99.9%) and initially 3.75 mol of C5-alcohol or C5-alcohol mixture Charge to a glass apparatus consisting of a stirred flask equipped with a stirrer, sampling port, dropping funnel, and water trap, connected to a forced cooler and thermometer. Flush the apparatus with nitrogen (6 l/h) through the sampling port for at least one hour. Then 0.51 g of tetra-n-butyl titanate (0.0015 mol) were added.

The reaction mixture was heated slowly to boiling temperature with stirring and a continuous nitrogen flow (6 l/h). From this point on, water is produced, which is continuously removed from the reaction by means of a water trap. After reaching a temperature of 240° C., a further 3.75 mol of C5-alcohol or mixture of C5-alcohols and 0.51 g of tetra-n-butyl titanate (0.0015 mol) are metered in via the dropping funnel and sampling port so that the reaction temperature does not drop to below 240°C. During the esterification, about 108 ml of water (6 mol of water of reaction) was produced. After this amount of water is reached, the acid value is occasionally determined from the reaction sample. The reaction was terminated after reaching an acid value of less than 0.1 mg KOH per g of sample and the resulting crude product was worked up as described below.

The crude product was poured into a stirred flask equipped with a stirrer, thermometer, dip tube, Claisen bridge, and receiving flask. Flush the unit with nitrogen (6 l/h) through the dip tube for at least one hour. 10 mol of water per mole of catalyst and 2% by weight of activated carbon (based on the total amount of product) were added to the crude product and the mixture was stirred at 80° C. under nitrogen for 15 minutes. The mixture was then heated slowly under maximum vacuum (<5 mbar) and the temperature increased to 160°C according to the onset of distillation. After completion of distillation of excess alcohol, the crude product was stripped under vacuum and nitrogen (20 mbar) introduced for 3 hours to further reduce the alcohol content. The mixture was then cooled back to 80°C and mixed with 2 wt% basic alumina (based on the total amount of product) and stirred for 1 hour. At this temperature, the product was then filtered under reduced pressure through a Büchner funnel filled with a pre-compacted filter cake of filter paper and filter aid (D14 Perlite) into a suction flask. The filtrate was the desired product (see Table 1).

Crude materials used: Table 1: Alcohols used and products obtainable therefrom sample Alcohol used Reaction time in hours t Purity of ester (GC in area %) Dynamic viscosity at 20°C in mPa*s A n-Pentanol/2-Methylbutanol (1:1) 9 99.3 69 B n-pentanol 9 99.1 46 2-Methylbutanol 7.5 99.2 121 3-Methylbutanol 8 99.2 76 3-Methylbutanol (3-Mb): Sigma Aldrich, >99% pure 2-Methylbutanol (2-Mb): Sigma Aldrich, >99% pure n-Pentanol (n-Pe): Sigma Aldrich, >99% Purity Example 2: Manufacture and Testing of Plastisols and Samples Made Therefrom

From the plasticizer synthesized according to Example 1, PVC plastisols were produced, as used, for example, for the production of surface coating films (without filler layer) for floor coverings. Amounts in plastisol formulations are each given in parts by mass (phr). The formulation is reported in Table 2. Table 2: Mixing ratios of manufactured plastisols substance Example number 1.1 1.2 1.3 1.4 1.5 100 100 100 100 100 50 A 50 B 50 50 50 3 3 3 3 3 Reagens CLX/759/6PF 2 2 2 2 2 Slurry-forming PVC from Vestolit GmbH Diisononyl phthalate (DINP) from Evonik Operations GmbH Drapex 39: Epoxidized soybean oil (ESBO) from Galata Chemicals Reagens CLX/759/6PF: Ca/Zn based Heat Stabilizer, from Reagens

The liquid ingredients were first weighed and placed into a mixing beaker, followed by the powdered ingredients weighed and placed into a mixing beaker, then stirred with a spatula to remove unwetted powder. The mixing beaker is then clamped in the dissolution stirrer. After starting the stirrer, slowly increase the speed to about 2000 rpm (revolutions per minute). During this time, the plastisol was carefully degassed. Once the plastisol reaches a temperature of about 30 °C, immediately reduce the speed to about 350 rpm. Afterwards, the plastisol was degassed for 9 minutes at this speed and a pressure below 20 mbar. This ensures that no immature fractions gel in the homogenization of the plastisol.

Examine various properties of the produced plastisols. Table 3 presents the results. Determination of plastisol viscosity

The viscosity of the manufactured plastisols was measured using a Physica MCR 101 rheometer (from Anton Paar Germany GmbH) with the assistance of associated software using the rotation mode and the CC27 measuring system. The measurements were made after the plastisols had equilibrated at 25°C for 24 hours from their manufacture.

The measurement includes the following points: - an initial shear at 100 s ^-1 for a period of up to 60 seconds, during which no measurement is made - a downward shear rate from 200 s ^-1 to 0.1 s ^-1 slope. Record 30 measurement points, each with a measurement point duration of 10 seconds.

The measurement is performed at room temperature. The viscosity measured in each example is the viscosity obtained at a shear rate of 100 s ^-1 . Table 3 lists the results of viscosity measurements for plastisols with the plasticizer or mixture of plasticizers specified in each example. Gelation properties

The gelling properties of plastisols were examined using a parallel plate analysis system (PP25) operating under shear pressure control in a Physica MCR 101 (from Anton Paar) in oscillatory mode. An additional temperature control hood was attached to the system to achieve the best heat distribution achievable. Establish the following measurement parameters: Mode: Temperature Gradient (Linear Temperature Ramp) Starting temperature: 25°C End temperature: 180°C Heating/cooling rate: 5 K/min Oscillation frequency: 4-0.1 Hz ramp (logarithmic) Cycle Frequency Omega: Number of measuring points: 63 Measuring point duration: 0.5 min Automatic Gap Adjustment Constant measuring point duration Gap width 0.5 mm Analysis program:

Use a spatula to apply a few drops of the plastisol to be analyzed to the lower plate of the analysis system. By this, it is possible to ensure that some plastisol seeps out of the analytical system evenly (not more than about 6 mm in any direction) after the analytical system is assembled. The temperature control hood is then placed over the sample and analysis is initiated. This includes determining the so-called complex viscosity of plastisols as a function of temperature. The onset of the gelling process is recognized by a sudden sharp rise in the complex viscosity. The earlier this viscosity increase starts, the better the gelling ability of the system. The measured curves obtained were used to determine the temperature at which the complex viscosity of 1000 Pa*s was measured for each plastisol by interpolation. The results are listed in Table 3. Determination of Shore A Hardness of Film

For the determination of the Shore hardness, the plastisol produced in Example 2 was poured into a circular stainless steel mold with a diameter of 42 mm (initial weight: 20 g). The slurry was then gelled in the mold at 200° C. for 25 min in an air-circulating drying oven, cooled and then removed and conditioned in a climate-controlled room (25° C.) for at least 16 hours, after which Measurement. The thickness of the obtained test specimens was about 12 mm.

The hardness measurement was carried out according to DIN 53 505 using a Shore A measuring instrument from Zwick-Roell; the measurement was read off after 3 seconds in each case. Measurements were taken at three different locations on each test specimen and an average value was formed. The results are listed in Table 3. Table 3: Results of the experiments performed nature Example number 1.1 1.2 1.3 1.4 1.5 Viscosity 100s ^-1 , after 24 h 6.67 11.3 8.24 17.2 9.15 Gelation (T in °C at 1000 Pa*s) 82 75 73 77 80 Shore A Hardness 80 75 74 78 80

Based on the results available, it can be found that the claimed compounds according to the above formula (I) or mixtures thereof exhibit results approximately comparable to DINP in terms of viscosity when used in plastisols. In some cases even significantly better results were achieved with regard to gelation temperature and Shore hardness. Compared to the corresponding 1,2,4-benzenetricarboxylates with the same alcohol composition, the viscosity in plastisols is significantly lower and thus the plastisols are more processable. Example 3 - Manufacture of Dry Blends

The test specimens required for the following examples were made by dry blending (dry blend manufacturing), calendering (rolling), and extruding the following formulations: Table 4: Mixing ratios of the manufactured dry blends substance Example number 2.1 2.2 2.3 2.4 2.5 100 100 100 100 100 67 A 67 B 67 67 67 3 3 3 3 3 2 2 2 2 2 0.4 0.4 0.4 0.4 0.4 PVC homopolymer from Inovyn Ba/Zn based heat stabilizer from Galata Calcium stearate from Galata

Using dry mixtures, known as dry blends, it is possible, for example, to manufacture cable and wire insulation, hose, or floor and roof membranes after thermoplastic processing such as calendering or extrusion. Dry blends were made in a Brabender turnover mixer.

Use the "Winmix" software to set the following parameters in the Brabender turnover mixer: Speed Program: Active Setting file: Speed 50 rpm; Hold time: 9 min; (Speed) rising time: 1 min; Speed 100 rpm; hold time: 20 min Temperature: 88°C Measuring range: 2 Nm Damping: 3

A temperature of 90°C was set on the thermostat and the temperature of the mixing vessel in the Brabender was controlled by a hose connection. After an equilibration period of one hour the temperature in the mixing vessel was 88°C. Immediately after the epicyclic mixer had been internally calibrated, the solid ingredients (PVC, stabilizer) previously weighed into the PE beaker were fed through the solids funnel and the filling stub present in the Brabender mixing vessel. The program was started and the powder mixture was stirred and heated in the mixing vessel for 9 minutes, after which the liquid ingredients were rapidly added within one minute through the liquid funnel and filling nipple if present. The mixture was stirred for an additional 20 minutes on an orbital mixer. At the end of the program, remove the finished dry mixture (powder). The transmitted torque-time graph was evaluated using Brabender software. A significant rise in the curve is evident after the addition of the liquid ingredients. Plasticizer absorption is complete only when the curve falls back significantly. The time difference between these two points is the plasticizer absorption time (the so-called dry mixing time). This and the maximum torque are automatically evaluated by the program (see Table 5).

These dry blends are used to make rolled sheet. Rolled sheets were made on a Collin W150 AP calender with automatic sample reverser and temperature controlled by an additional oil thermostat. Controlled by Collin software.

A five-stage process is used to manufacture rolled sheet: stage name temperature [°C] Duration [s] Gap width [mm] speed [rpm] 1 Plasticization of dry blends 165 60 0.2 5 2 increase in gap size 165 30 0.5 20 3 Start of sample inverter 165 170 0.5 20 4 Rolled sheet optimization 165 30 0.5 25 5 Rolled sheet removal 165 60 0.5 7

After the rolling temperature is achieved, the rolling gap is corrected. As a starting measurement, the roll gap was adjusted to 0.2 mm. 160 g of each dry blend was weighed out and introduced into the nip with the rolls stationary and the program started.

Extruded panels were fabricated using a Collin laboratory extruder. Use pre-rolled sheet (see above) to make extruded board. The side edges of the rolled sheet were removed using a cutting machine, and then the rolled sheet was cut into small pieces with a size of about 14.5 x 14.5 cm. For extruded plates with a thickness of 1 mm, in each case 2 small pieces of rolled sheet were placed one on top of the other and placed in a stainless steel extruded frame measuring 15 x 15 cm.

Use the following three-stage procedure to manufacture extruded panels: stage name temperature [°C] pressure [bar] Duration [s] 1 initial squeeze 170 5 60 2 squeeze 170 200 200 3 cool down 40 200 200

Various tests were carried out on the manufactured extruded panels. Table 5 presents the results.

The Shore A hardness was determined as described in Example 2, but here as test specimens were produced extruded plates with a thickness of 6 mm. For this purpose, in each case 12 rolled sheet pellets were placed in a stainless steel extrusion frame measuring 5 x 5 cm. Glass transition temperature of extruded plate (Tg)

The glass transition temperature was determined by DMTA measurement according to DIN 65583 using a MCR 302 rheometer from Anton Paar. Under constant dynamic mechanical conditions (1 Hz, deformation 0.3%), record the viscoelastic properties of the film (1 mm thickness) with temperature change (temperature ramp -100 to +50°C) and measure the storage modulus and loss modulus , and loss factor. In this example the maximum value of the loss modulus is interpreted as the glass transition temperature. The table below shows the average of duplicate determinations in each case. Table 5: Results of the experiments performed nature Example number 2.1 2.2 2.3 2.4 2.5 Plasticizer absorption time in s 5.4 4.3 3.7 4.9 5.2 Tg in °C -36 -26 -33 -20 -18 Shore A Hardness 71 66 65 67 69

In the examples of dry blends produced and test specimens produced therefrom, the results show that better results can be achieved in all examples using the compounds according to the invention according to formula (I) above or mixtures thereof. Specifically, the plasticizer absorption time and Shore A hardness were significantly improved compared to DINP; the glass transition temperature was significantly lower compared to the corresponding 1,2,4-benzenetricarboxylate with the same alcohol composition.

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Claims (14)

A plasticizer composition comprising at least one compound according to the following formula (I)

(I) wherein the groups R ₁ , R ₂ , and R ₃ are each independently selected from the group consisting of n-pentyl, 2-methylbutyl, and 3-methylbutyl. The plasticizer composition according to claim 1, wherein the groups R ₁ , R ₂ , and R ₃ are the same. The plasticizer composition according to claim 1, which comprises a mixture of compounds according to formula (I)

(I) wherein present in the mixture is a group from the group consisting of n-pentyl, 2-methylbutyl, and 3-methylbutyl in a proportion of 30 to 95 mol%, and A further radical or two further radicals from the groups specified in a proportion of 5 to 70 mol %, in each case based on all radicals R ₁ , R ₂ , and R ₃ . Such as the plasticizer composition of claim 3, wherein those present in the mixture are composed of n-pentyl, 2-methylbutyl, and 3-methylbutyl in a ratio of 40 to 95 mol%. and one radical from the group specified and one or two further radicals from the specified group in a proportion of 5 to 60 mol%, based in each case on the totality of the compounds according to formula (I) Groups R ₁ , R ₂ , and R ₃ . The plasticizer composition as claimed in claim 3 or 4, wherein the 2-methylbutyl group is present in the mixture in a proportion of a maximum of 60 mol%, preferably in a proportion of a maximum of 40 mol%, in each case All radicals R ₁ , R ₂ , and R ₃ based on compounds according to formula (I). The plasticizer composition according to any one of claims 1 to 5, wherein the plasticizer composition comprises alkyl benzoate, dialkyl adipate, glyceride, trialkyl citrate Esters, acylated trialkyl citrate, diol dibenzoate, trialkyl 1,2,4-benzenetricarboxylic acid, dialkyl terephthalate, dialkyl phthalate, difuran Esters of carboxylic acids, dialkylyl esters of dianhydrohexitol (such as isosorbide), epoxidized fatty acid alkyl esters, polymeric plasticizers, such as polyadipates, and further plasticizers of the group consisting of dialkyl esters of 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid. The plasticizer composition as claimed in item 6, wherein the other plasticizer is selected from C8- to C13-alkyl benzoate, C4- to C10-dialkyl adipate, C4 to C9-alkane Trialkyl citrate, C4- to C10-trialkyl 1,2,4-benzenetricarboxylate, C4- to C9-dialkyl terephthalate, C4- to C13- Dialkyl esters, especially C9- to C13-dialkyl phthalates, and C4- to C10-dialkyl esters of 1,2-, 1,3- or 1,4-cyclohexanedicarboxylic acid composed of groups. A plasticizer composition according to any one of the preceding claims, which, in addition to the at least one compound according to the above formula (I) or a mixture of compounds according to the above formula (I), also contains 1,2- or 1,4 - cyclohexanedicarboxylates, especially the corresponding diisononyl esters or di-2-ethylhexyl esters. As the plasticizer composition of claims 1 to 7, it still comprises di-ethylhexyl terephthalate ( DOTP). The plasticizer composition as claimed in items 1 to 7, which, in addition to the at least one compound according to the above formula (I) or a mixture of compounds according to the above formula (I), also contains dibutyl terephthalate, para Di(iso)pentyl phthalate, isodecyl benzoate, isononyl benzoate, acetyl tributyl citrate, tributyl citrate, dipropylene glycol dibenzoate, diethylene dibenzoate A fast-gelling plasticizer of the group consisting of alcohol esters, triethylene glycol dibenzoate, and mixtures of two or more thereof. Use of a plasticizer composition according to any one of the preceding claims as a plasticizer for polymers. As the use of claim 11, it is used for PVC or vinyl chloride-containing polymers. A plastic composition comprising one or more polyvinyl chloride, a copolymer of vinyl chloride and vinyl acetate or butyl acrylate, polyalkyl methacrylate (PAMA), polyvinyl butyral (PVB), Polymers of the group consisting of polyurethane, polysulfide, polylactic acid (PLA), polyhydroxybutyraldehyde (PHB), and nitrocellulose, and plastics according to any one of claims 1 to 7 chemical composition. The plastic composition according to claim 13, wherein the plastic composition contains at least PVC as a polymer.